Two-component diazotype photosensitive material

ABSTRACT

TWO-COMPONENT DIAZOTYPE PHOTOSENSITIVE MATERIAL CONTAINING A COUPLIN COMPONENT OF THE FOLLOWING GENERAL FORMULA 1 AND A DIAZOCOMPOUND OF THE FOLLOWING GENERAL FORMULA 2 GIVES A NAVY BLUE OR DARK BLUE DYE-IMAGE HAVING HIGH DENSITY AND FASTNESS BY DEVELOPING IN AN ALKALINE SOLUTION OR VAPOR.   1-(2,4-(NH=)-2,3,4,5-TETRAHYDRO-TRIAZIN-5-YL),7-(HO-),   8-(R2-N(-R1)-CH2-)NAPHTHALENE (1)   1-((-C-C)&gt;N-),2-(R3-O-),4-(X-N*N-),5-(R4-O-)BENZENE (2)

United States- Patent US. Cl. 96-91 R 8 Claims ABSTRACT OF THEDISCLOSURE Two-component diazotype photosensitive material containing acoupling component of the following general Formula 1 and adiazocompound of the following general Formula 2 gives a navy blue ordark blue dye-image having high density and fastness by developing in analkaline solution or vapor.

EH e 6 F III HC\ /O=NH CH2 N BACKGROUND OF THE INVENTION (A) Field ofthe invention The present invention relates to two-component diazotypephotosensitive material containing a compound having the followinggeneral Formula 1 as a coupling component:

provide two-component diazotype photosensitive material capable ofgiving a dye-image of high density and fastness.

3,667,955 Patented June 6, 1972 SUMMARY OF THE INVENTION The presentinvention relates to two-component diazotype photosensitive materialcontaining a coupling component and a diazocompound in a photosensitivelayer, and capable of developing in an alkaline solution or vapor andgiving a vivid dye-image of high density and fastness.

The compounds having a following general Formula 1 are used as acoupling component and these coupling components are novel and have notbeen disclosed in the literature.

The general formula of the aforementioned coupling component is asfollows:

wherein R and R are the same or different alkyl radical of from 1 to 4carbon atoms, or they may be linked together with nitrogen to complete aheterocyclic ring system which may be contain one or more substituents.

These coupling components are very soluble in water, do not cause tocoagulate with diazocompounds to produce a clear photosensitivesolution, do not contaminate the substrate of the photosensitivematerial and give a vivid dye-image of high density and fastness whencoupled with a suitable diazocompound.

The examples of these coupling components are in following:

l- 2',4-diimino-3 '-hydro- 1 ,3 ,5'-triaz.ino) -7-hydroxy-8-dimethylaminomethyl-naphthalene (=MJP'. 209- 211 C.),

1-(2,4'-diimino-3-hydro-1',3,5'-triazino)-7-hydroxy-8-diethylaminomethyl-naphthalene (M.P. 209-2l21-(27,4-diimino-3'-hydro-1',3,5'-triazino)-7-hydroxy-8-dipropylaminomethyl-naphthalene (M.P. 2l 12l2 1- (2',4'-diimino-3-hydrol ',3 ',5 '-triazino) -7-hydroxy- 8-dibutylaminomethyl-naphthalene(M.P. 21 l213 l-(2',4-diimino-3'-hydro-1',3',5'-triazino)-7-hydroxy-8-morpholinomethyl-naphthalene (M.P. 214-215l-(2,4'-diimino-3'-hydro-l',3',5'-triazino)-7-hydroxy-8-piperazinomethyl-naphthalene (M.P. 2l4215 C.),l-(2',4'-diimino-3-hydro-1,3,5'triazino)-7-hydroxy-8-piperidinomethyl-naphthalene (M.P. 213-214 C.).

A method of producing one of the above-mentioned compounds is, forexample, as follows:

l-biguanidino-7-naphthol (sold by American Hoechst Co. under thetrademark Coupler 8) causes ring closure condensation by the reactionwith formic acid to give 1- (2',4' diimino3'-hydro-l',3',5-triazino)-7-hydroxynaphthalene. This compound, 9 g.(0.033 mol), is suspended in 50 cc. of alcohol and then 10.5 g. (0. 05mol) of dimorpholinomethane are added thereto. This mixture is boiledunder reflux for about 4 hours. Ash-colored crystals are separated andfiltered off. The crude product thus obtained (1d g., M.P. 209-211 C.)are recrystallized from methyl alcohol to give White crystals (9 g.,

3 M.P. 214-215 C.) of 1-(2',4'-dihnino-3'-hydro=1,3',S'-triazino)-7-hydroxy8-morpholinomethyl-naphthalene.

The preferred diazocornpounds which give a navy blue or dark bluedye-image having high density and fastness when coupled with theaforementioned coupling components, are those having the followinggeneral Formula 2:

wherein R and R are the same or different alkyl radicals of from 1 to 5carbon atoms,

is a substituted or unsubstituted heterocyclic ring system and X is ananion.

Typical diazocompounds having said general formula are, for example, asfollow:

Sulfates of the above cited compounds may be also advantageously used.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention isfurther illustrated by the following examples.

. EXAMPLE 1 A photosensitive solution was prepared from the followingingredients:

Water: 1,000 cc.

Citric acid: 20 g.

Ammonium citrate: g.

Ethylene glycol: 30 g.

1 (2',4'-diimino-3'hydro-1',3,5'-triazino)-7-hydroXy-8-morpholinomethyl-naphthalene: 28 g.

l morpholino 2,5 dibutoxy-4-diazobenzene chloride /2ZnCl 12 g.

Sapom'n: 1 g.

Methylene Blue: 0.05 g.

This solution was applied to a support (e.g. paper or sheet) and thendried off. The two-component diazotype photosensitive material thusobtained gave a vivid navy blue dye-image of high density, whenirradiated with light in contact with an image original and subjected todevelopment in the developing solution prepared from the followingingredients:

Water: 1,000 cc.

Potassium carbonate: 20 g. Potassium tetraborate: 30 g. Thiourea: 20 g.

The printed material did not show discoloration and fading.

Said photosensitive material gave also a navy 'blue dyeimage of highdensity by developing in an ammonia vapor.

4 EXAMPLE 2 A photosensitive solution was prepared from the followingingredients:

Water: 1,000 cc.

Cone. H 5 cc.

Cadmium sulfate: 10 g.

Thiourea: 10 g. I

l (2',4'-diimino-3'-hydro-1',3,5'-triazino) 7 hydroxy-8-dimethylaminomethyl-naphthalene: 20 g.

l-piperazino 2,5 diamyloxy 4 diazobenzene chloride /zZnCl 10 g.

Saponin: 1 g.

Methylene Blue: 0.05 g.

This solution was applied to a substrate, precoated with an aqueoussuspension prepared from the following ingredients, and then dried oif.

Water: 1,000 cc.

Corn starch (particle size I-S g. Colloidal silica (particle size1-5;.L)2 40 g. Vinyl acetate emulsion (solid 50% 80 g.

The photosensitive material thus obtained gave a blue dye-image of highdensity by developing in an 5% aqueous solution of potassium metaborateand also gave a dyeimage of good contrast by developing in an ammoniavapor.

EXAMPLE 3 The procedure of Example 1 was repeated except that 1morpholino 2,5 diethoxy 4 diazobenzene chloride /zZnCl was used as asubstitute for 1-morpholino-2,5- dibutoxy-tdiazdbenzene chloride /2ZnCland the same dye-image as that of Example 1 was obtained.

EXAMPLE 4 A photosensitive solution was prepared from the followingingredients:

Water: 1,000 cc.

Oxalic acid: 5 g.

Cone. H 80 1 cc.

Cadmium sulfate: 10 g.

Thiourea: 10 g.

1-(2,4 diimino 3' hydro 1,3',5' t-riazino) 7hydroxy-8-piperidinomethyl-naphthalene: 25 g.

1-morpholino-2,5-dibutoxy-4-diazobenzene sulfate: 11 g.

Saponin: l g.

Methylene blue: 0.05 g.

The photosensitive material prepared from this solution gave a bluedye-image of higher density than that of Example 1.

EXAMPLE 5 The procedure of Example 2 was repeated except that1-(2',4'-diimino 3 hydro 1',3',5'-triazino)-7-hydroxy-8-dibutylaminomethyl-naphthalene as a substitute for 1- (2,4'-d iirnino3' hydro 1',3',5' triazino)-7-hydroxy- 8 dimethylaminomethyl naphthaleneand the same dyeimage as that of Example 2.

What is claimed is:

1. A two-component diazotype photosensitive material comprising asupport having a coating thereon wherein the coating contains (a) acoupling component having the following formula:

wherein R and R are the same or different alkyl radicals of from 1 to 4carbon atoms and when taken together, with the nitrogen atom to whichthey are attached, form a 5 or 6 member saturated heterocyclic ring and(b) a diazonium compound of the formula:

wherein R and R are the same or diiferent alkyl radicals of from 1 to 5carbon atoms,

as defined in claim 1 wherein said coupling component is 3 1-(2',4'diimino 3' hydro 1',3',5triazino)-7-hydroxy-8-dipropylaminomethyl-naphthalene.

5. A two-component diazotype photosensitive material as defined in claim1 wherein said coupling component is 1-(2,4'-diimino-3-hydro-1,3',5'-triazin0) 7 hydr0xy-8-dibutylaminomethyl-naphthalene.

6. A two-component diazotype photosensitive material as defined in claim1 wherein said coupling component is1-(2,4-diimino-3-hydro-1',3',5'-triazino) 7 hydroxy-8-morpholinomethyl-naphthalene.

7. A two-component diazotype photosensitive material as defined in claim1 wherein said coupling component is l-(2',4' diimino '3' hydro 1',3',5'triazino)-7-hydroxy-8-piperazinomethyl-naphthalene.

8. A two-component diazotype photosensitive material as defined in claim1 wherein said coupling component is1-(2,4'-diimino-3'-hydro-1',3',5'-triazino) 7 hydroxy-8-piperidinomethyl-naphthalene.

References Cited UNITED STATES PATENTS 2,150,565 3/1939 Schmidt et al.96-91 X 2,437,691 3/1948 Grun 260-2499 3,343,960 9/1967 Sus 96-913,493,378 2/1970 Sus 96-91 FOREIGN PATENTS 864,951 1/1953 Germany 96-91OTHER REFERENCES Bann et al., Chem. Reviews, vol. 58, February 1958, pp.131-134 relied on.

CHARLES L. BOWERS, JR., Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,667,955 Dated June 6, 1972 Inventor(s) Shigeaki Yoshida, et a1 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In the specification:

In column 3, line 55, chance "28g" to -25g- In the claims:

In claim 1, lines 6-10, change the formula to v v read -OR in'place of"OR".

Signed and sealed this 24th day of April 1973.

(SEAL) Attest:

EDWARD M.FLETC IHER,JR. ROBERT GOTTSCHALK Attestlng Offlcer Commissionerof Patents

